Threshold of Surface Initiator Concentration for Polymer Brush Growth by Surface-Initiated Atom Transfer Radical Polymerization

The surface modification of various materials by grafting functional molecules has attracted much attention from fundamental research to practical applications because of its ability to impart various physical and chemical properties to the surfaces. One promising approach is the use of polymer brushes synthesized by atom transfer radical polymerization (ATRP) from surface-tethered initiators (SIs). In this study, for the purpose of controlling the grafting amounts/densities of polymer brushes, we developed a facile method to precisely regulate SI concentrations of SI layers (SILs) by serial dilution based on a sol-gel method. By simply mixing organosilanes terminated with and without an initiator group ((p-chloromethyl) phenyltrimethoxysilane (CMPTMS) and phenyltrimethoxysilane (PTMS), respectively) with tetraethoxysilane (TEOS), SI concentrations of SILs could be arbitrarily tuned precisely by varying dilution factors of (CMPTMS + PTMS)/CMPTMS (DFs, 1-107). The resulting SILs prepared at different DFs were highly smooth and transparent. X-ray photoelectron spectroscopy (XPS) also confirmed that the SIs were homogeneously distributed at the topmost surface of the SILs and their concentrations were proven to be accurately and precisely controlled from high to extremely low, comparable to theoretical values. Subsequent SI-ATRP in air ("paint-on" SI-ATRP) of two different types of monomers (hydrophobic/nonionic (2,3,4,5,6-pentafluorostyrene) and hydrophilic/ionic (sodium 4-styrenesulfonate)) demonstrated that polymer brushes with different grafting amounts/densities were successfully grafted only from SILs with DFs of 1-104 (theoretical SI concentrations: 3.9 × 10-4 ∼ 3.5 units/nm2), while at DFs of 105 and above (theoretical SI concentrations: <3.9 × 10-5 units/nm2), no sign of polymer brush growth was confirmed by thickness, XPS, and water contact angle data. Therefore, we are the first to gather evidence that the approximate threshold of SI concentration required for "paint-on" SI-ATRP might be on the order of 10-4 ∼ 10-5 units/nm2.